JPWO2004049458A1 - Photoelectric conversion element - Google Patents

Abstract

An organic compound (A) having both an electron donating molecular structure and an electron accepting molecular structure as a photoelectric conversion layer used in a photoelectric conversion element useful for a solar power generation device or a solar power generation system, and / or an electron donating property By using a photoelectric conversion layer in which an organic compound (B) having a molecular structure and an organic compound (C) having an electron-accepting molecular structure are dispersed in a polymer, phase separation of the photoelectric conversion layer is suppressed and light is emitted. A photoelectric conversion element with improved utilization efficiency is provided.

Description

  The present invention relates to a photoelectric conversion element useful for a solar power generation device, a solar power generation system, and the like.

In recent years, due to increasing awareness of environmental problems, solar energy, which is an inexpensive and clean energy resource, has attracted attention as a fossil fuel that emits carbon dioxide, which is said to have an impact on global warming. Converting solar energy into other energy, for example, electric energy, is important for its effective use, and inorganic semiconductor photovoltaic elements such as silicon have been developed and put into practical use. However, these photovoltaic devices have enormous energy to manufacture, and it is desired to develop photoelectric conversion devices that can be manufactured at lower costs with lower energy.
Organic compounds are inexpensive, and even if they are disposed of by incineration after use, the burden on the environment is small. Against this background, the development of photoelectric conversion elements using organic photoelectric conversion materials is one of the most important energy measures.
The photoelectric conversion element using organic matter is of interest from the fact that the Tang element in 1986 showed about 1% efficiency (Applied Physics Letters, Vol. 48, January 13, 1986, p. 183-185). The photoelectric conversion efficiency has been improved year after year. In an organic photoelectric conversion element, it is necessary to make a so-called heterojunction structure by combining an electron-donating organic semiconductor (donor) and an electron-accepting organic semiconductor (acceptor). Effective charge separation occurs near the donor-acceptor interface. Based on this idea, so-called bulk heterojunction in which a donor conductive polymer and an acceptor fullerene derivative are mixed has been proposed (for example, US Pat. No. 5,454,880 and US Pat. No. 5,454,880), and a higher density donor. / A photoelectric conversion element having an acceptor interface has been developed, and its photoelectric conversion efficiency has increased. Thus, the recent development of organic photoelectric conversion elements is how to design the charge separation interface between the donor and the acceptor.
In addition, efficient transport of carriers (electrons, holes) generated after charge separation is an important development point for high efficiency. Friend et al. Succeeded in creating a structure with high carrier transfer efficiency by using an electron-donating benzocoronene stacking by self-assembly and an electron-accepting perylene dye (Science, 293, 2001 8). 10 May, p. 1119-1122). Stacking of the π-conjugated system shows a large carrier mobility in the stacking direction.
On the other hand, the strong tendency of molecules to be self-organized may cause phase separation because the same molecules of the donor and the acceptor gather when producing a photoelectric conversion element. When phase separation occurs, irregularities occur on the surface of the photoelectric conversion layer, leading to a decrease in photoelectric conversion efficiency.
The present invention has been made in view of such a situation, and relates to a photoelectric conversion material capable of suppressing phase separation and producing a good photoelectric conversion layer, and a photoelectric conversion element using the photoelectric conversion material.

一般式（１）〜（６１）中、Ｒ^６〜Ｒ^６０（Ｒ^１０およびＲ^１２を除く）は各々同一でも異なっていてもよく、各々個別に、水素原子、直鎖もしくは分岐した炭素数１〜１０のアルキル基、アルケニル基、アルコキシル基、または炭素数６〜１２のアリール基、アラルキル基、アリールオキシ基を示す。なお、Ｒ^４４はシクロペンタジエニル環と結合し、環を形成してもよいし、互いに異なるシクロペンタジエニル環を架橋する基を形成してもよい。
Ｒ^１０およびＲ^１２は各々同一でも異なっていてもよく、各々個別に、水素原子、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、アミノ基、カルボキシル基、アセチル基、ホルミル基、直鎖もしくは分岐した炭素数１〜１０のアルキル基、アルケニル基、アルコキシル基、アルキルチオ基、アルキルオキシカルボニル基、または炭素数６〜１２のアリール基、アラルキル基、アリールオキシ基を示す。
また、同一構造式中に、複数のＲ^６〜Ｒ^６０が存在する場合、それらは同一でも異なってもよい。
Ａ⁻およびＢ⁻は各々同一でも異なっていてもよく、各々個別に、ハロゲンアニオン、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻およびＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻から選ばれる対アニオンを示す。
また、ｍ、ｎは、各々１〜１０００、好ましくは２〜５００の整数を表し、ｋ、ｌは、各環状炭化水素基の置換可能数を表すものであり、通常各々０〜４の整数の範囲である。
Ｍ^１はＣｕ、Ｚｎ、Ｃｏ、Ｆｅ、Ｔｉ、Ｍｇ、Ｎｉ、Ｍｏ、Ｏｓ、Ｒｕなどの金属原子を表す。Ｍ^２はＬｉ、Ｎａ、Ｍｇ、Ｃａ等のアルカリ金属あるいはアルカリ土類金属を表す。Ｍ^３はＣｒ、Ｃｏ、Ｆｅ、Ｍｇ、Ｎｉ、Ｏｓ、Ｒｕ、Ｖ、Ｘ−Ｈｆ−Ｙ、Ｘ−Ｍｏ−Ｙ、Ｘ−Ｎｂ−Ｙ、Ｘ−Ｔｉ−Ｙ、Ｘ−Ｖ−ＹまたはＸ−Ｚｒ−Ｙを示す。なお、ここでいうＸおよびＹは水素、ハロゲンまたは炭素数１〜１２のアルキル基を表し、互いに同一でも異なっていてもよい。
前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ｉ−プロピル基、ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などが挙げられ、アルケニル基としては、ビニル基、アリル基、イソプロペニル基、ブチレニル基、ペンチレニル基、ヘキセニル基などが挙げられ、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ｉ−プロポキシ基、ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ペントキシ基、イソペントキシ基、ネオペンチルオキシ基、ｔ−ペンチルオキシ基、ヘキシルオキシ基、イソヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基等が挙げられ、アリール基としては、フェニル基、キシリル基、トリル基、クメニル基、ナフチル基等が、アラルキル基としては、ベンジル基、トリメチル基等が、アリールオキシ基としては、フェノキシ基、トリルオキシ基などが挙げられる。
電子供与性分子構造と電子受容性分子構造を併有する化合物では、上述したような電子供与性分子構造と電子受容性分子構造が共有結合やイオン結合のような化学結合により結合している。共有結合としては、例えば、炭素数１〜２０、好ましくは１〜１０の炭化水素基による結合が挙げられ、これらの具体例としてアルキレン等の炭化水素基の他、エステル結合含有炭化水素基、エーテル結合含有炭化水素基、アミド結合含有炭化水素基、チオエーテル結合含有炭化水素基、アミン結合含有炭化水素基、ウレタン結合含有炭化水素基、シリル結合含有炭化水素基などが好適なものとして挙げることができる。
電子受容性分子構造と電子供与性分子構造の好適な組み合わせとしては、フラーレン誘導体（式（３））とポリ（フェニレンビニレン）誘導体（式（４０））、シアノ基含有ポリ（フェニレンビニレン）誘導体（式（４））とポリ（フェニレンビニレン）誘導体（式（４０））、ビオロゲン誘導体（式（１））とアミン誘導体（式（２９）〜（３５））、ビオロゲン誘導体（式（１））とメタロセン誘導体（式（４６））、ビオロゲン誘導体（式（１））とポリチオフェン誘導体（式（４２））、ビオロゲン誘導体（式（１））とポリピロール誘導体（式（４２））、ビオロゲン誘導体（式（１））とポリ（フェニレンビニレン）誘導体（式（４０））、ペリレン誘導体（式（２））と銅フタロシアニン誘導体（式（２０）〜（２２））、ペリレン誘導体（式（２））とフタロシアニン誘導体（式（１９））、ペリレン誘導体（式（２））とアミン誘導体（式（２９）〜（３５））、ペリレン誘導体（式（２））とポリ（フェニレンビニレン）誘導体（式（４０））、ペリレン誘導体（式（２））とポリチオフェン誘導体（式（４２））、ペリレン誘導体（式（２））とポリピロール誘導体（式（４２））、ペリレン誘導体（式（２））とメタロセン誘導体（式（４６））、フラーレン誘導体（式（３））と銅フタロシアニン誘導体（式（２０）〜（２２））、フラーレン誘導体（式（３））とアミン誘導体（式（２９）〜（３５））、フラーレン誘導体（式（３））とポリチオフェン誘導体（式（４２））、フラーレン誘導体（式（３））とポリピロール誘導体（式（４２））、フラーレン誘導体（式（３））とメタロセン誘導体（式（４６））、シアノ基含有ポリ（フェニレンビニレン）誘導体（式（４））とアミン誘導体（式（２９）〜（３５））、シアノ基含有ポリ（フェニレンビニレン）誘導体（式（４））と銅フタロシアニン誘導体（式（２０）〜（２２））、シアノ基含有ポリ（フェニレンビニレン）誘導体（式（４））とポリチオフェン誘導体（式（４２））、シアノ基含有ポリ（フェニレンビニレン）誘導体（式（４））とポリピロール誘導体（式（４２））、シアノ基含有ポリ（フェニレンビニレン）誘導体（式（４））とメタロセン誘導体（式（４６））などの組み合わせが好ましい。
このような化合物の例としては、下記式（６２）〜（６６）に示すようなものが挙げられる。

一般式（６２）〜（６６）中、Ｒ^６、Ｒ^９、Ｒ^１０、Ｒ^１２〜Ｒ^１４、Ｒ^１６およびＲ^３８は各々同一でも異なっていてもよく、各々個別に、直鎖および分岐した炭素数１〜１０のアルキル基、アルケニル基、アルコキシル基または炭素数６〜１２のアリール基、アラルキル基、アリールオキシ基、アラルキル基を示す。Ｒ^{１ ５}は炭素数１〜２０、好ましくは１〜１０の２価の炭化水素基を示す。Ａ⁻およびＢ⁻は各々同一でも異なっていてもよく、各々個別に、ハロゲンアニオン、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻およびＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻から選ばれる対アニオンを示す。また、ｍ、ｎは、各々１〜１０００、好ましくは２〜５００の整数を表し、ｋ、ｌは、各環状炭化水素基の置換可能数を表すものであり、通常各々０〜４の整数の範囲である。
一般式（６２）〜（６６）におけるＲ^１５の炭化水素基の好適な具体例としてはアルキレン等の炭化水素基の他、エステル結合含有炭化水素基、エーテル結合含有炭化水素基、アミド結合含有炭化水素基、チオエーテル結合含有炭化水素基、アミン結合含有炭化水素基、ウレタン結合含有炭化水素基、シリル結合含有炭化水素基などが挙げられる。
前記エステル結合含有炭化水素基としては一般式−Ｒ−ＣＯＯ−Ｒ’−または−Ｒ−ＯＣＯ−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜８のアルキレンを示す。）で表されるものが挙げられ、エーテル結合含有炭化水素基としては一般式−Ｒ−Ｏ−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜１０のアルキレンを示す。）で表されるものが挙げられ、アミド結合含有炭化水素基としては一般式−Ｒ−ＣＯＮＨ−Ｒ’−または−Ｒ−ＮＨＣＯ−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜８のアルキレンを示す。）で表されるものが挙げられ、チオエーテル結合含有炭化水素基としては一般式−Ｒ−Ｓ−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜１０のアルキレンを示す。）で表されるものが挙げられ、アミン結合含有炭化水素基としては一般式−Ｒ−ＮＨ−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜１０のアルキレンを示す。）で表されるものや一般式−Ｒ−ＮＨ−Ｐｈ−基（Ｒは炭素数１〜１０のアルキレンを示し、Ｐｈは炭素数６〜１２のアリーレン基あるいは置換アリーレン基を示す。）が挙げられ、ウレタン結合含有炭化水素基としては一般式−Ｒ−ＯＣＯＮＨ−Ｒ’−または−Ｒ−ＮＨＣＯＯ−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜８のアルキレンを示す。）で表されるものが挙げられ、シリル結合含有炭化水素基としては一般式−Ｒ−Ｓｉ（Ｒ”）_２−Ｒ’−（ＲおよびＲ’はそれぞれ炭素数１〜８のアルキレンを示し、Ｒ”はメチル基またはエチル基を示す。）で表されるものが挙げられる。
なかでも、これらの化合物として、具体的には、下記に示す化合物が好適なものとして挙げられる。

また、具体的な電子受容性分子構造を有する化合物の例としては下記式（１’）〜（１８’）に示すものを、また電子供与性分子構造を有する化合物の例としては下記式（１９’）〜（６１’）に示すものを挙げることができる。

一般式（１’）〜（６１’）中、Ｒ^１〜Ｒ^９およびＲ^１３〜Ｒ^６０は各々同一でも異なっていてもよく、各々個別に、水素原子、直鎖もしくは分岐した炭素数１〜１０のアルキル基、アルケニル基、アルコキシル基、または炭素数６〜１２のアリール基、アラルキル基、アリールオキシ基を示す。なお、Ｒ^４４はシクロペンタジエニル環と結合し、環を形成してもよいし、互いに異なるシクロペンタジエニル環を架橋する基を形成してもよい。
Ｒ^１０〜Ｒ^１２は各々同一でも異なっていてもよく、各々個別に、水素原子、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、アミノ基、カルボキシル基、アセチル基、ホルミル基、直鎖もしくは分岐した炭素数１〜１０のアルキル基、アルケニル基、アルコキシル基、アルキルチオ基、アルキルオキシカルボニル基、または炭素数６〜１２のアリール基、アラルキル基、アリールオキシ基を示す。
また、同一構造式中に、複数のＲ^１〜Ｒ^６０が存在する場合、それらは同一でも異なってもよい。
Ａ⁻およびＢ⁻は各々同一でも異なっていてもよく、各々個別に、ハロゲンアニオン、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻およびＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻から選ばれる対アニオンを示す。
また、ｍ、ｎは、各々１〜１０００、好ましくは２〜５００の整数を表し、ｋ、ｌは、各環状炭化水素基の置換可能数を表すものであり、通常各々０〜４の整数の範囲である。
Ｍ^１はＣｕ、Ｚｎ、Ｃｏ、Ｆｅ、Ｔｉ、Ｍｇ、Ｎｉ、Ｍｏ、Ｏｓ、Ｒｕなどの金属原子を表す。Ｍ^２はＬｉ、Ｎａ、Ｍｇ、Ｃａ等のアルカリ金属あるいはアルカリ土類金属を表す。Ｍ^３はＣｒ、Ｃｏ、Ｆｅ、Ｍｇ、Ｎｉ、Ｏｓ、Ｒｕ、Ｖ、Ｘ−Ｈｆ−Ｙ、Ｘ−Ｍｏ−Ｙ、Ｘ−Ｎｂ−Ｙ、Ｘ−Ｔｉ−Ｙ、Ｘ−Ｖ−ＹまたはＸ−Ｚｒ−Ｙを示す。なお、ここでいうＸおよびＹは水素、ハロゲンまたは炭素数１〜１２のアルキル基を表し、互いに同一でも異なっていてもよい。
前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ｉ−プロピル基、ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などが挙げられ、アルケニル基としては、ビニル基、アリル基、イソプロペニル基、ブチレニル基、ペンチレニル基、ヘキセニル基などが挙げられ、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ｉ−プロポキシ基、ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ペントキシ基、イソペントキシ基、ネオペンチルオキシ基、ｔ−ペンチルオキシ基、ヘキシルオキシ基、イソヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基等が挙げられ、アリール基としては、フェニル基、キシリル基、トリル基、クメニル基、ナフチル基等が、アラルキル基としては、ベンジル基、トリメチル基等が、アリールオキシ基としては、フェノキシ基、トリルオキシ基などが挙げられる。
電子受容性分子構造を有する化合物および電子供与性分子構造を有する化合物の具体例としては、ポリアセチレン、ポリピロール、ポリピリジン、ポリ−ｐ−フェニレン、ポリ−ｐ−フェニレンスルフィド、ポリフェニレンビニレン、ポリ（２，５−ジヘキシロキシ−１，４−フェニレンビニレン）、ポリ（２，５−ジオクチロキシ−１，４−フェニレンビニレン）、ポリ（２−メトキシ−５−（２’−エチルヘキシロキシ）−１，４−フェニレンビニレン）および以下に示す化合物（６９）〜（１３１）等などが好適なものとして挙げられる。

電子受容性分子構造と電子供与性分子構造の好適な組み合わせとしては、フラーレン誘導体（上記式（３’））とポリ（フェニレンビニレン）誘導体（上記式（４０’））、シアノ基含有ポリ（フェニレンビニレン）誘導体（上記式（４’））とポリ（フェニレンビニレン）誘導体（上記式（４０’））、ビオロゲン誘導体（上記式（１’））とアミン誘導体（上記式（２９’）〜（３５’））、ビオロゲン誘導体（上記式（１’））とメタロセン誘導体（上記式（４６’））、ビオロゲン誘導体（上記式（１’））とポリチオフェン誘導体（上記式（４２’））、ビオロゲン誘導体（上記式（１’））とポリピロール誘導体（上記式（４２’））、ビオロゲン誘導体（上記式（１’））とポリ（フェニレンビニレン）誘導体（上記式（４０’））、ペリレン誘導体（上記式（２’））と銅フタロシアニン誘導体（上記式（２０’）〜（２２’））、ペリレン誘導体（上記式（２’））とフタロシアニン誘導体（上記式（１９’））、ペリレン誘導体（上記式（２’））とアミン誘導体（上記式（２９’）〜（３５’））、ペリレン誘導体（上記式（２’））とポリ（フェニレンビニレン）誘導体（上記式（４０’））、ペリレン誘導体（上記式（２’））とポリチオフェン誘導体（上記式（４２’））、ペリレン誘導体（上記式（２’））とポリピロール誘導体（上記式（４２’））、ペリレン誘導体（上記式（２’））とメタロセン誘導体（上記式（４６’））、フラーレン誘導体（上記式（３’））と銅フタロシアニン誘導体（上記式（２０’）〜（２２’））、フラーレン誘導体（上記式（３’））とアミン誘導体（上記式（２９’）〜（３５’））、フラーレン誘導体（上記式（３’））とポリチオフェン誘導体（上記式（４２’））、フラーレン誘導体（上記式（３’））とポリピロール誘導体（上記式（４２’））、フラーレン誘導体（上記式（３）’）とメタロセン誘導体（上記式（４６’））、シアノ基含有ポリ（フェニレンビニレン）誘導体（上記式（４’））とアミン誘導体（上記式（２９’）〜（３５’））、シアノ基含有ポリ（フェニレンビニレン）誘導体（上記式（４’））と銅フタロシアニン誘導体（上記式（２０’）〜（２２’））、シアノ基含有ポリ（フェニレンビニレン）誘導体（上記式（４’））とポリチオフェン誘導体（上記式（４２’））、シアノ基含有ポリ（フェニレンビニレン）誘導体（上記式（４’））とポリピロール誘導体（上記式（４２）’）、シアノ基含有ポリ（フェニレンビニレン）誘導体（上記式（４’））とメタロセン誘導体（上記式（４６’））などの組み合わせが好ましい。
また、光電変換層を構成するポリマー中に分散されるこれらの電子供与性分子構造および電子受容性分子構造を兼備する化合物（Ａ）、あるいはまた電子供与性分子構造を有する化合物（Ｂ）または電子受容性分子構造を有する化合物（Ｃ）は、さらに導電性を具備することが望ましい。これらの化合物が導電性を有するか否かについては常法により容易に判別することができる。例えば、これらの化合物に、ドーピングを行った後、常法により電気伝導度を測定することにより判別することができる。通常、電気伝導度が１０^−６〜１０^６Ｓ／ｍ、好ましくは１０^−４〜１０^５Ｓ／ｃｍ程度のものが望ましい。
本発明においては、光電変換層を構成するポリマー中に電子供与性分子構造と電子受容性分子構造を併有する化合物（Ａ）、および／または電子供与性分子構造を有する化合物（Ｂ）および電子受容性分子構造を有する化合物（Ｃ）を分散させることを特徴とする。分散方法としては、特に限定されないが、ホモジナイザー、ボールミル、ビーズミル、サンドミル、２本ロール、３本ロール等を用いた分散方法が挙げられ、必要に応じて本発明を損なわない範囲で、適当な溶媒を用い、該溶媒に各成分を分散または溶解する方法も挙げられる。
なお、ポリマー前駆体と、電子供与性分子構造と電子受容性分子構造を有する化合物（Ａ）、および／または電子供与性分子構造を有する化合物（Ｂ）および電子受容性分子構造を有する化合物（Ｃ）を予め分散処理したのち、常法によりポリマー前駆体を重合しポリマー化してもよい。
またこの光電変換層を形成する導電基板としては、適当な方法により導電性が得られれば特に制限されることはないが、通常は、透明基板上に透明電極層を積層させて製造される。透明基板としては、特に限定されず、材質、厚さ、寸法、形状等は目的に応じて適宜選択することができ、例えば無色あるいは有色ガラス、網入りガラス、ガラスブロック等が用いられる他、無色あるいは有色の透明性を有する樹脂でも良い。具体的には、ポリエチレンテレフタレートなどのポリエステル、ポリアミド、ポリスルホン、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリフェニレンサルファイド、ポリカーボネート、ポリイミド、ポリメチルメタクリレート、ポリスチレン、トリ酢酸セルロース、ポリメチルペンテンなどが挙げられる。なお、本発明における透明とは、１０〜１００％の透過率を有することであり、また、本発明における基板とは、常温において平滑な面を有するものであり、その面は平面あるいは曲面であってもよく、また応力によって変形するものであってもよい。
また、透明電極層を形成する透明導電膜としては、本発明の目的を達成するものである限り特に限定されないが、例えば金、銀、クロム、銅、タングステンなどの金属薄膜、金属酸化物からなる導電膜などが挙げられる。金属酸化物としては、例えば、酸化錫、酸化亜鉛や、これらに微量成分をドープしたＩｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ（ＩＴＯ（Ｉｎ_２Ｏ_３：Ｓｎ））、Ｆｌｕｏｒｉｎｅ ｄｏｐｅｄ Ｔｉｎ Ｏｘｉｄｅ（ＦＴＯ（ＳｎＯ_２：Ｆ））、Ａｌｕｍｉｎｕｍ ｄｏｐｅｄ Ｚｉｎｃ Ｏｘｉｄｅ（ＡＺＯ（ＺｎＯ：Ａｌ））などが好適なものとして用いられる。これらの膜厚は通常、１００〜５０００ｎｍ、好ましくは５００〜３０００ｎｍである。また、表面抵抗（抵抗率）は、本発明の基板の用途により適宜選択されるところであるが、通常、０．５〜５００Ω／ｓｑ、好ましくは２〜５０Ω／ｓｑである。
透明電極膜の形成法としては、特に限定されなく、導電層として用いる前述の金属や金属酸化物の種類により適宜公知の方法が選択使用されるところであるが、通常、真空蒸着法、イオンプレーティング法、ＣＶＤあるいはスパッタリング法などが用いられる。いずれの場合も基板温度２０〜７００℃の範囲内で形成されるのが望ましい。
また、必要に応じて、導電基板と光電変換層の間に半導体層を設けてもよい。半導体層を作製するのに用いられる材料としては、Ｂｉ_２Ｓ_３、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＣｕＩｎＳ_２、ＣｕＩｎＳｅ_２、Ｆｅ_２Ｏ_３、ＧａＰ、ＧａＡｓ、ＩｎＰ、Ｎｂ_２Ｏ_５、ＰｂＳ、Ｓｉ、ＳｎＯ_２、ＴｉＯ_２、ＷＯ_３、ＺｎＯ、ＺｎＳ等が挙げられ、好ましくはＣｄＳ、ＣｄＳｅ、ＣｕＩｎＳ_２、ＣｕＩｎＳｅ_２、Ｆｅ_２Ｏ_３、ＧａＡｓ、ＩｎＰ、Ｎｂ_２Ｏ_５、ＰｂＳ、ＳｎＯ_２、ＴｉＯ_２、ＷＯ_３、ＺｎＯであり、これらを複数組み合わせて用いてもよい。特に好ましくはＴｉＯ_２、ＺｎＯ、ＳｎＯ_２、Ｎｂ_２Ｏ_５であり、最も好ましくはＴｉＯ_２、ＺｎＯである。
用いる半導体は単結晶でも多結晶でも良い。結晶系としては、アナターゼ型、ルチル型、ブルッカイト型などが主に用いられるが、好ましくはアナターゼ型である。半導体層の形成には公知の方法を用いることができる。
半導体層の形成方法としては、上記半導体のナノ粒子分散液、ゾル溶液等を、公知の方法により基板上に塗布することで得ることが出来る。この場合の塗布方法としては特に限定されずキャスト法による薄膜状態で得る方法、スピンコート法、ディップコート法、バーコート法のほか、スクリーン印刷法を初めとした各種の印刷方法を挙げることができる。
半導体層の厚みは任意であるが０．５μｍ以上５０μｍ以下、好ましくは１μｍ以上２０μｍ以下である。
さらに本発明の光電変換素子では、必要に応じて、電子障壁層及び／または正孔輸送層や正孔障壁層及び／または電子輸送層や保護層を設けることもできる。電子障壁層及び／または正孔輸送層は、通常陽極と光電変換層の間に設けられ、正孔障壁層及び／または電子輸送層は、通常と陰極と光電変換層の間に設けられる。これらの層構造の一例を図２に示す。
電子障壁層及び正孔輸送層に用いられる材料は、光生成した正孔を輸送する機能あるいは光生成した電子を障壁する機能のいずれかを有しているものであればよい。その具体例としては、カルバゾール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三級アミン化合物、スチリルアミン化合物、芳香族ジメチリディン系化合物、ポルフィリン系化合物、ポリシラン系化合物、ポリ（Ｎ−ビニルカルバゾール）誘導体、アニリン系共重合体、チオフェンオリゴマーやポリチオフェン等の導電性高分子等が挙げられる。
電子障壁層及び／または正孔輸送層は１種又は２種以上の上記材料からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
電子障壁層及び／または正孔輸送層の形成方法としては、真空蒸着法、ＬＢ法、インクジェット法、上記材料を溶媒中に溶解又は分散させて塗布する方法（スピンコート法、キャスト法、ディップコート法等）等が用いられる。
塗布する方法の場合、上記材料を樹脂成分と共に溶解又は分散させて塗布液を調製してもよく、該樹脂成分としては、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリメチルメタクリレート、ポリブチルメタクリレート、ポリエステル、ポリスルホン、ポリフェニレンオキシド、ポリブタジエン、ポリ（Ｎ−ビニルカルバゾール）、炭化水素樹脂、ケトン樹脂、フェノキシ樹脂、ポリアミド、エチルセルロース、ポリ酢酸ビニル、ＡＢＳ樹脂、ポリウレタン、メラミン樹脂、不飽和ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、シリコン樹脂等が使用できる。電子障壁層及び正孔輸送層の膜厚は特に限定されないが、通常１ｎｍ〜５μｍとするのが好ましく、５ｎｍ〜１μｍとするのがより好ましく、１０ｎｍ〜５００ｎｍとするのが特に好ましい。
正孔障壁層及び／または電子輸送層に用いられる材料は、光生成した電子を輸送する機能あるいは光生成した正孔を障壁する機能のいずれかを有しているものであればよい。その具体例としては、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、フルオレノン誘導体、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド誘導体、フルオレニリデンメタン誘導体、ジスチリルピラジン誘導体、ナフタレンペリレン等の複素環テトラカルボン酸無水物、フタロシアニン誘導体、金属錯体（８−キノリノール誘導体の金属錯体、メタルフタロシアニン、ベンゾオキサゾールやベンゾチアゾールを配位子とする金属錯体等）等が挙げられる。
正孔障壁層及び／または電子輸送層は１種又は２種以上の上記材料からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
正孔障壁層及び／または電子輸送層の形成方法としては、真空蒸着法、ＬＢ法、インクジェット法、上記材料を溶媒中に溶解又は分散させて塗布する方法（スピンコート法、キャスト法、ディップコート法等）等が用いられる。
塗布する方法の場合、上記材料を樹脂成分と共に溶解又は分散させて塗布液を調製してもよい。該樹脂成分としては、前述した電子障壁層及び／または正孔輸送層の場合と同様のものが使用できる。正孔障壁層及び／または電子輸送層の膜厚は特に限定されず、通常１ｎｍ〜５μｍとするのが好ましく、５ｎｍ〜１μｍとするのがより好ましく、１０ｎｍ〜５００ｎｍとするのが特に好ましい。
保護層は水分、酸素等の素子劣化を促進するものが素子内に入ることを抑止する機能を有する。保護層の材料としては、金属（Ｉｎ、Ｓｎ、Ｐｂ、Ａｕ、Ｃｕ、Ａｇ、Ａｌ、Ｔｉ、Ｎｉ等）、金属酸化物（ＭｇＯ、ＳｉＯ、ＳｉＯ_２、Ａｌ_２Ｏ_３、ＧｅＯ、ＮｉＯ、ＣａＯ、ＢａＯ、Ｆｅ_２Ｏ_３、Ｙ_２Ｏ_３、ＴｉＯ_２等）、金属フッ化物（ＭｇＦ_２、ＬｉＦ、ＡｌＦ_３、ＣａＦ_２等）、ポリエチレン、ポリプロピレン、ポリメチルメタクリレート、ポリイミド、ポリウレア、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリジクロロジフルオロエチレン、クロロトリフルオロエチレンとジクロロジフルオロエチレンとの共重合体、テトラフルオロエチレンと少なくとも１種のコモノマーとを含むモノマー混合物を共重合させて得られる共重合体、共重合主鎖に環状構造を有する含フッ素共重合体、吸水率１％以上の吸水性物質、吸水率０．１％以下の防湿性物質等が使用できる。
保護層の形成方法は特に限定されず、真空蒸着法、スパッタリング法、反応性スパッタリング法、ＭＢＥ（分子線エピタキシ）法、クラスターイオンビーム法、イオンプレーティング法、プラズマ重合法（高周波励起イオンプレーティング法）、プラズマＣＶＤ法、レーザーＣＶＤ法、熱ＣＶＤ法、ガスソースＣＶＤ法、塗布法、インクジェット法等が適用できる。
また、光電変換層の薄膜上に形成する導電膜としてはアルミニウム、マグネシウム、金、銀、白金、インジウム、銅、クロムなどの金属や、マグネシウム：銀などの合金の他、導電性のカーボンや銀、金、銅等の金属ペースト等が挙げられる。
この導電膜の形成方法としては導電膜として用いる前述の材料により適宜公知の方法が選択使用されるところであるが、通常、真空蒸着法、イオンプレーティング法、ＣＶＤあるいはスパッタリング法等のドライ成膜やスピンコート法、ディップコート法、バーコート法、ディスペンサー法のほか、スクリーン印刷法を初めとした各種の印刷方法を挙げることができる。
導電膜の膜厚は、通常１００〜５０００μｍ、好ましくは５００〜３０００μｍである。また、表面抵抗（抵抗率）は、本発明の光電変換素子の用途により適宜選択されるところであるが、通常、０．５〜５００Ω／ｓｑ、好ましくは２〜５０Ω／ｓｑである。
また、本発明の光電変換素子の別の態様として、対極基板を用いて、対向基板、電子供与性分子構造および電子受容性分子構造を有する化合物（Ａ）、および／または電子供与性分子構造を有する化合物（Ｂ）および電子受容性分子構造を有する化合物（Ｃ）が分散したポリマーからなる光電変換層および導電性基板を積層する形態をとることもできる。
対極基板としては、それ自体で導電性を有する支持基板、または支持基板上に導電膜を形成したものを挙げることが出来る。
支持基板としては、特に限定されず、材質、厚さ、寸法、形状等は目的に応じて適宜選択することができる。支持基板には導電性があっても無くてもよく、金、白金などの金属のほか、例えば無色あるいは有色ガラス、網入りガラス、ガラスブロック等が用いられる他、無色あるいは有色の透明性を有する樹脂でも良い。具体的には、ポリエチレンテレフタレートなどのポリエステル、ポリアミド、ポリスルホン、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリフェニレンサルファイド、ポリカーボネート、ポリイミド、ポリメチルメタクリレート、ポリスチレン、トリ酢酸セルロース、ポリメチルペンテンなどが挙げられる。
なお、本発明における基板とは、常温において平滑な面を有するものであり、その面は平面あるいは曲面であってもよく、また応力によって変形するものであってもよい。また、支持基板表面には金、白金などの金属や、Ｉｎ_２Ｏ_３：Ｓｎ、ＳｎＯ_２：Ｆ、ＺｎＯ：Ａｌなどの薄膜を真空蒸着法、電子ビーム真空蒸着法、スパッタリング法等の公知の方法で成膜し、対極基板とすることができる。
対極基板を用いる場合には、光電変換層と対極基板の間に、電解質層を設けても良い。電解質層は（ａ）高分子マトリックス、（ｂ）可塑剤、（ｃ）支持電解質、から選ばれる少なくとも１種以上の物質を含有してなるイオン伝導性材料であって、上記（ａ）〜（ｃ）あるいは（ｄ）レドックス剤によって可逆な酸化還元特性を示すことを特徴とする。
高分子マトリックスとして使用できる材料としては、高分子マトリックス単体で、あるいは可塑剤の添加や、支持電解質の添加、または可塑剤と支持電解質の添加によって固体状態またはゲル状態が形成されれば特に制限は無く、一般的に用いられるいわゆる高分子化合物を用いることができる。
上記高分子マトリックスとしての特性を示す高分子化合物としては、具体的には、ヘキサフロロプロピレン、テトラフロロエチレン、トリフロロエチレン、エチレン、プロピレン、アクリロニトリル、塩化ビニリデン、アクリル酸、メタクリル酸、メチルアクリレート、エチルアクリレート、メチルメタクリレート、スチレンポリフッ化ビニリデンなどのモノマーを重合あるいは共重合させて得られる高分子化合物を挙げることができる。またこれらの高分子化合物は単独で用いても、混合して用いても良い。
可塑剤としては、一般に電気化学セルや電池に用いられる溶媒であればいずれも使用することができる。具体的には、無水酢酸、メタノール、エタノール、テトラヒドロフラン、プロピレンカーボネート、ニトロメタン、アセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホアミド、エチレンカーボネート、ジメトキシエタン、γ−ブチロラクトン、γ−バレロラクトン、スルホラン、ジメトキシエタン、プロピオンニトリル、グルタロニトリル、アジポニトリル、メトキシアセトニトリル、ジメチルアセトアミド、メチルピロリジノン、ジメチルスルホキシド、ジオキソラン、スルホラン、リン酸トリメチル、リン酸トリエチル、リン酸トリプロピル、リン酸エチルジメチル、リン酸トリブチル、リン酸トリペンチル、リン酸トリヘキシル、リン酸トリヘプチル、リン酸トリオクチル、リン酸トリノニル、リン酸トリデシル、リン酸トリス（トリフフロロメチル）、リン酸トリス（ペンタフロロエチル）、リン酸トリフェニルポリエチレングリコール、及びポリエチレングリコール等が使用可能である。特に、プロピレンカーボネート、エチレンカーボネート、ジメチルスルホキシド、ジメトキシエタン、アセトニトリル、γ−ブチロラクトン、スルホラン、ジオキソラン、ジメチルホルムアミド、ジメトキシエタン、テトラヒドロフラン、アジポニトリル、メトキシアセトニトリル、ジメチルアセトアミド、メチルピロリジノン、ジメチルスルホキシド、ジオキソラン、スルホラン、リン酸トリメチル、リン酸トリエチルが好ましい。可塑剤はその１種を単独で使用しても良いし、また２種以上を混合して使用しても良い。
支持電解質としては、電気化学の分野又は電池の分野で通常使用される塩類、酸類、アルカリ類、常温溶融塩類が使用できる。
塩類としては、特に制限はなく、例えば、アルカリ金属塩、アルカリ土類金属塩等の無機イオン塩；４級アンモニウム塩；環状４級アンモニウム塩；４級ホスホニウム塩などが使用でき、特にＬｉ塩が好ましい。
塩類の具体例としては、ハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、および（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻から選ばれる対アニオンを有するＬｉ塩、Ｎａ塩、あるいはＫ塩が挙げられる。
またハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、および（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻から選ばれる対アニオンを有する４級アンモニウム塩、具体的には、（ＣＨ_３）_４ＮＢＦ_４、（Ｃ_２Ｈ_５）_４ＮＢＦ_４、（ｎ−Ｃ_４Ｈ_９）_４ＮＢＦ_４、（Ｃ_２Ｈ_５）_４ＮＢｒ、（Ｃ_２Ｈ_５）_４ＮＣｌＯ_４、（ｎ−Ｃ_４Ｈ_９）_４ＮＣｌＯ_４、ＣＨ_３（Ｃ_２Ｈ_５）_３ＮＢＦ_４、（ＣＨ_３）_２（Ｃ_２Ｈ_５）_２ＮＢＦ_４、（ＣＨ_３）_４ＮＳＯ_３ＣＦ_３、（Ｃ_２Ｈ_５）_４ＮＳＯ_３ＣＦ_３、（ｎ−Ｃ_４Ｈ_９）_４ＮＳＯ_３ＣＦ_３、さらには、

等が挙げられる。またハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、および（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻から選ばれる対アニオンを有するホスホニウム塩、具体的には、（ＣＨ_３）_４ＰＢＦ_４、（Ｃ_２Ｈ_５）_４ＰＢＦ_４、（Ｃ_３Ｈ_７）_４ＰＢＦ_４、（Ｃ_４Ｈ_９）_４ＰＢＦ_４等が挙げられる。
また、これらの混合物も好適に用いることができる。
酸類も特に限定されず、無機酸、有機酸などが使用でき、具体的には硫酸、塩酸、リン酸類、スルホン酸類、カルボン酸類などが使用できる。
アルカリ類も特に限定されず、水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどがいずれも使用可能である。
常温溶融塩類も特に限定されることは無いが、本発明における常温溶融塩とは、溶媒成分が含まれないイオン対のみからなる常温において溶融している（即ち液状の）イオン対からなる塩であり、通常、融点が２０℃以下であり、２０℃を越える温度で液状であるイオン対からなる塩を示す。
常温溶融塩はその１種を単独で使用することができ、また２種以上を混合しても使用することもできる。
常温溶融塩の例としては、例えば、以下のものが挙げられる。

（ここで、Ｒは炭素数２〜２０、好ましくは２〜１０のアルキル基を示す。Ｘ⁻はハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、および（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻から選ばれる対アニオンを表す。）

（ここで、Ｒ１およびＲ２は各々炭素数１〜１０のアルキル基（好ましくはメチル基またはエチル基）、または炭素数７〜２０、好ましくは７〜１３のアラルキル基（好ましくはベンジル基）を示しており、互いに同一でも異なっても良い。また、Ｘ⁻は対アニオンを示し、具体的にはハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻などを示す。）

（ここで、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は、各々炭素数１以上、好ましくは炭素数１〜６のアルキル基、炭素数６〜１２のアリール基（フェニル基など）、またはメトキシメチル基などを示し、互いに同一でも異なってもよい。また、Ｘ⁻は対アニオンを示し、具体的にはハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻など示す。）
以上の支持電解質の使用量については特に制限はなく、任意であるが、通常、電解質層中に０．１質量％以上、好ましくは１質量％以上、さらに好ましくは１０質量％以上であり、かつ７０質量％以下、好ましくは６０質量％以下、さらに好ましくは５０質量％以下の量で含有させることができる。
次に、レドックス材について説明する。
レドックス材は可逆な電気化学的酸化還元反応を行うことができるものであって、特にその種類を制限するものではない。レドックス材は、酸化体、還元体のどちらか一方のみを用いてもよいし、酸化体と還元体を適当なモル比で混合し、添加することもできる。
また、高分子マトリックス、可塑剤、支持電解質が電気化学的応答性を示すように、これら高分子マトリックス、可塑剤、支持電解質の酸化還元対を添加するなどしても良い。そのような性質を示す材料として、ハロゲンイオン、ＳＣＮ⁻、ＣｌＯ_４ ⁻、ＢＦ_４ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＣＨ_３ＣＯＯ⁻、ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、および（Ｃ_２Ｆ_５ＳＯ_２）_３Ｃ⁻から選ばれる対アニオンを有するフェロセニウムなどのメタロセニウム塩などのほか、ヨウ素、臭素、塩素などのハロゲン類を用いることもできる。
電解質には、更に他の成分を含有させることができる。含有させることができる他の成分としては、紫外線吸収剤を挙げることができる。用いることができる紫外線吸収剤としては、特に限定されないが、ベンゾトリアゾール骨格を有する化合物、ベンゾフェノン骨格を有する化合物等の有機紫外線吸収剤が代表的なものとして挙げられる。
ベンゾトリアゾール骨格を有する化合物としては、例えば、下記の一般式（１３２）で表される化合物が好適に挙げられる。

一般式（１３２）において、Ｒ^８１は、水素原子、ハロゲン原子または炭素数１〜１０、好ましくは１〜６のアルキル基を示す。ハロゲン原子としてはフッ素、塩素、臭素、ヨウ素を挙げることができる。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ｉ−プロピル基、ブチル基、ｔ−ブチル基、シクロヘキシル基等を挙げることができる。Ｒ^８１の置換位置は、ベンゾトリアゾール骨格の４位または５位であるが、ハロゲン原子およびアルキル基は通常４位に位置する。Ｒ^８２は、水素原子または炭素数１〜１０、好ましくは１〜６のアルキル基を示す。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ｉ−プロピル基、ブチル基、ｔ−ブチル基、シクロヘキシル基等を挙げることができる。Ｒ^８３は、炭素数１〜１０、好ましくは１〜３のアルキレン基またはアルキリデン基を示す。アルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基等を挙げることができ、またアルキリデン基としては、例えば、エチリデン基、プロピリデン基等が挙げられる。
一般式（１３２）で示される化合物の具体例としては、３−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ−ベンゼンプロパン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ−ベンゼンエタン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−４−ヒドロキシベンゼンエタン酸、３−（５−メチル−２Ｈ−ベンゾトリアゾール−２−イル）−５−（１−メチルエチル）−４−ヒドロキシベンゼンプロパン酸、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ビス（α，α−ジメチルベンジル）フェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、３−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ−ベンゼンプロパン酸オクチルエステル等が挙げられる。
ベンゾフェノン骨格を有する化合物としては、例えば、下記の一般式（１３３）〜（１３５）で示される化合物が好適に挙げられる。

上記一般式（１３３）〜（１３５）において、Ｒ^９２、Ｒ^９３、Ｒ^９５、Ｒ^９６、Ｒ^９８、及びＲ^９９は、互いに同一もしくは異なる基であって、ヒドロキシル基、炭素数１〜１０、好ましくは１〜６のアルキル基またはアルコキシ基を示す。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ｉ−プロピル基、ブチル基、ｔ−ブチル基、及びシクロヘキシル基を挙げることができる。またアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ｉ−プロポキシ基、及びブトキシ基を挙げることができる。
Ｒ^９１、Ｒ^９４、及びＲ^９７は、炭素数１〜１０、好ましくは１〜３のアルキレン基またはアルキリデン基を示す。アルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、及びプロピレン基を挙げることができる。アルキリデン基としては、例えば、エチリデン基、及びプロピリデン基が挙げられる。
ｐ１、ｐ２、ｐ３、ｑ１、ｑ２、及びｑ３は、それぞれ別個に０乃至３の整数を表す。
上記一般式（１３３）〜（１３５）で表されるベンゾフェノン骨格を有する化合物の好ましい例としては、２−ヒドロキシ−４−メトキシベンゾフェノン−５−カルボン酸、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン−５−カルボン酸、４−（２−ヒドロキシベンゾイル）−３−ヒドロキシベンゼンプロパン酸、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２’−カルボキシベンゾフェノン等が挙げられる。
もちろん、これらを二種以上組み合わせて使用することができる。
紫外線吸収剤の使用は任意であり、また使用する場合の使用量も特に制限されるものではないが、使用する場合は電解質中に０．１質量％以上、好ましくは１質量％以上であり、２０質量％以下、好ましくは１０質量％以下の範囲の量で含有させることが望ましい。
電解質層は電解質フィルムとして製造しても良い。電解質フィルムの製造方法について以下に説明する。
電解質フィルムは、所望により可塑剤、支持電解質、レドックス材、紫外線吸収剤等の任意成分を高分子マトリックス成分中に配合することにより得られる混合物を、公知の方法によりフィルムに成形することにより得ることが出来る。この場合の成形方法としては特に限定されず、押出し成型、キャスト法によるフィルム状態で得る方法、スピンコート法、ディップコート法などを挙げることができる。
押出し成型については常法により行うことができ、高分子マトリックスと可塑剤、支持電解質、レドックス材、紫外線吸収剤等の任意成分を混合し、過熱溶融した後、フィルム成型することが行われる。
キャスト法については、高分子マトリックスと可塑剤、支持電解質、レドックス材、紫外線吸収剤等の任意成分を混合し、さらに適当な希釈剤にて粘度調整を行い、キャスト法に用いられる通常のコータにて塗布し、乾燥することで成膜することができる。コータとしては、ドクタコータ、ブレードコータ、ロッドコータ、ナイフコータ、リバースロールコータ、グラビアコータ、スプレイコータ、カーテンコータを用いることができ、粘度および膜厚により使い分けることができる。
スピンコート法については、高分子マトリックスと可塑剤、支持電解質、レドックス材、紫外線吸収剤等の任意成分を混合し、さらに適当な希釈剤にて粘度調整を行い、市販のスピンコーターにて塗布し、乾燥することで成膜することができる。
ディップコート法については、高分子マトリックスと可塑剤、支持電解質、レドックス材、紫外線吸収剤等の任意成分を混合し、さらに適当な希釈剤にて粘度調整を行って混合物溶液を作製し、適当な基盤を混合物溶液より引き上げた後、乾燥することで成膜することができる。
以上の方法により得られた電解質フィルムは、イオン伝導度が、通常室温で１×１０^−７Ｓ／ｃｍ以上、好ましくは１×１０^−６Ｓ／ｃｍ以上、さらに好ましくは１×１０^−５Ｓ／ｃｍ以上を示す。イオン伝導度は、複素インピーダンス法などの一般的な手法で求めることができる。
電解質フィルムの厚さは、特に限定されないが、下限としては、通常１μｍ以上、好ましくは１０μｍ以上であり、上限としては通常３ｍｍ以下、好ましくは１ｍｍ以下である。  As a result of the study by the present inventors, the photoelectric conversion layer is composed of a polymer, and by dispersing a specific compound in the polymer, the occurrence of phase separation in the photoelectric conversion layer can be suppressed and the light utilization efficiency can be increased. The present inventors have found that a photoelectric conversion element having excellent performance that can be obtained is obtained, and have completed the present invention.
  That is, the present invention relates to a photoelectric conversion element having a photoelectric conversion layer in which an organic compound (A) having both an electron donating molecular structure and an electron accepting molecular structure is dispersed in a polymer.
  The present invention also provides a photoelectric conversion layer comprising a photoelectric conversion layer in which an organic compound (B) having an electron-donating molecular structure and an organic compound (C) having an electron-accepting molecular structure are dispersed in a polymer. The present invention relates to a conversion element.
  The present invention is described in detail below.
  First, the polymer which comprises a photoelectric converting layer in the photoelectric conversion element of this invention is demonstrated. The polymer used in the present invention can disperse an organic compound (A) having both an electron-donating molecular structure and an electron-accepting molecular structure (hereinafter also simply referred to as compound (A)), or electron-donating. An organic compound (B) having an ionic molecular structure (hereinafter also simply referred to as compound (B)) and an organic compound (C) having an electron-accepting molecular structure (hereinafter also simply referred to as compound (C)) are dispersed. There is no particular limitation as long as it can be used. Examples include acrylic polymers such as polymethyl methacrylate and polyethyl acrylate, polyethers such as polyethylene oxide and polypropylene oxide, polyesters such as polyethylene terephthalate, and conductive polymer compounds such as polyphenylene vinylene, polyacetylene, polythiophene, and polypyrrole. It is done. Among these, a conductive polymer compound is particularly preferable. The conductive polymer compound is usually 10^-6-10⁶S / cm, preferably 10^-4-10⁵What has the electrical conductivity (20 degreeC) of S / cm is preferable.
  The molecular weight of the polymer is not particularly limited as long as the compound (A) can be dispersed, or the compound (B) and the compound (C) can be dispersed and a photoelectric conversion layer can be formed. Selected. Usually, 1,000 to 5,000,000, preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000 are used.
  The content of the organic compound (A) having both the electron-donating molecular structure and the electron-accepting molecular structure in the polymer is not particularly limited as long as the object of the present invention is not impaired, but usually 5 to 100 parts by mass of the polymer. 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass.
  Further, the contents of the organic compound (B) having an electron donating molecular structure and the organic compound (C) having an electron accepting molecular structure in the polymer are not particularly limited as long as the object of the present invention is not impaired. The organic compound (B) having an electron-donating molecular structure is usually 5 to 300 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 80 parts by weight, based on the part by weight. The organic compound (C) is usually 5 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass. Moreover, although the usage-ratio of the organic compound (B) which has an electron-donating molecular structure and the organic compound (C) which has an electron-accepting molecular structure is not specifically limited, Usually, mass ratio of both is 10 / 90-90 / 10, preferably 20/80 to 80/20.
  In the present invention, the electron donating molecular structure refers to a structure having a small ionization potential and a property that tends to be positive ions by supplying electrons to other molecules. In the present invention, the electron accepting molecular structure The term “structure” refers to a structure that has a high electron affinity and that receives electrons from other molecules and tends to be in a negative ionic state.
  In the present invention, when the compound (A) having both an electron donating molecular structure and an electron accepting molecular structure is used, the above-mentioned electron accepting or electron donating properties are relative to each other in the compound (A). The combination of structures satisfying these properties is appropriately selected depending on the specific relationship.
  In the present invention, when the compound (B) having an electron-donating molecular structure and the compound (C) having an electron-accepting molecular structure are used in combination, the above-described electron-accepting or electron-donating properties are those used. These are naturally determined by the relative relationship between the compounds, and a combination of compounds satisfying these properties is appropriately selected.
  The molecular structure having an electron donating property used in the present invention is not particularly limited as long as it has an electron donating property in the molecular structure part. For example, an amine structure, a metallocene structure, a polyarylene vinylene structure, Examples thereof include a polyaniline structure, a polythiophene structure, a polypyrrole structure, and a polyamine structure.
  Further, the molecular structure having electron accepting property is not particularly limited as long as it has electron accepting property, and examples thereof include a viologen structure, a perylene structure, and a fullerene structure.
  Specific examples of molecular structures having electron accepting properties are those shown in the following formulas (1) to (18), and examples of electron donating molecular structures are those shown in the following formulas (19) to (61). Can be mentioned.

  In general formulas (1) to (61), R⁶~ R⁶⁰(R¹⁰And R¹²Each may be the same or different, and each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxyl group, or an aryl group having 6 to 12 carbon atoms, An aralkyl group and an aryloxy group are shown. R⁴⁴May combine with a cyclopentadienyl ring to form a ring, or may form a group that bridges different cyclopentadienyl rings.
  R¹⁰And R¹²Each may be the same or different, and each independently represents a hydrogen atom, halogen atom, cyano group, nitro group, hydroxyl group, amino group, carboxyl group, acetyl group, formyl group, linear or branched carbon number 1 to 10 alkyl groups, alkenyl groups, alkoxyl groups, alkylthio groups, alkyloxycarbonyl groups, or aryl groups, aralkyl groups, and aryloxy groups having 6 to 12 carbon atoms.
  In the same structural formula, a plurality of R⁶~ R⁶⁰May be the same or different.
  A⁻And B⁻May be the same or different, and each independently represents a halogen anion, ClO.₄ ⁻, BF₄ ⁻, PF₆ ⁻, CH₃COO⁻And CH₃(C₆H₄) SO₃ ⁻The counter anion chosen from is shown.
  M and n each represent an integer of 1 to 1000, preferably 2 to 500, and k and l represent the number of substitutable substituents of each cyclic hydrocarbon group. It is a range.
  M¹Represents a metal atom such as Cu, Zn, Co, Fe, Ti, Mg, Ni, Mo, Os, Ru. M²Represents an alkali metal or alkaline earth metal such as Li, Na, Mg, and Ca. M³Is Cr, Co, Fe, Mg, Ni, Os, Ru, V, X—Hf—Y, X—Mo—Y, X—Nb—Y, X—Ti—Y, X—V—Y or X—Zr. -Y is shown. In addition, X and Y here represent hydrogen, a halogen, or a C1-C12 alkyl group, and may mutually be same or different.
  Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, and hexyl. Group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Examples of the alkenyl group include vinyl group, allyl group, isopropenyl group, butyryl group, pentylenyl group, hexenyl group and the like. As the group, methoxy group, ethoxy group, propoxy group, i-propoxy group, butoxy group, s-butoxy group, t-butoxy group, pentoxy group, isopentoxy group, neopentyloxy group, t-pentyloxy group, hexyloxy Group, isohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group Group, decyloxy group and the like, as aryl group, phenyl group, xylyl group, tolyl group, cumenyl group, naphthyl group and the like, as aralkyl group, benzyl group, trimethyl group and the like as aryloxy group, A phenoxy group, a tolyloxy group, etc. are mentioned.
  In a compound having both an electron-donating molecular structure and an electron-accepting molecular structure, the electron-donating molecular structure and the electron-accepting molecular structure as described above are bonded by a chemical bond such as a covalent bond or an ionic bond. Examples of the covalent bond include a bond with a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include hydrocarbon groups such as alkylene, ester bond-containing hydrocarbon groups, ethers. Preferred examples include a bond-containing hydrocarbon group, an amide bond-containing hydrocarbon group, a thioether bond-containing hydrocarbon group, an amine bond-containing hydrocarbon group, a urethane bond-containing hydrocarbon group, and a silyl bond-containing hydrocarbon group. .
  Suitable combinations of the electron-accepting molecular structure and the electron-donating molecular structure include fullerene derivatives (formula (3)) and poly (phenylene vinylene) derivatives (formula (40)), cyano group-containing poly (phenylene vinylene) derivatives ( Formula (4)) and poly (phenylene vinylene) derivatives (Formula (40)), viologen derivatives (Formula (1)) and amine derivatives (Formulas (29) to (35)), viologen derivatives (Formula (1)) and Metallocene derivative (formula (46)), viologen derivative (formula (1)) and polythiophene derivative (formula (42)), viologen derivative (formula (1)) and polypyrrole derivative (formula (42)), viologen derivative (formula ( 1)) and a poly (phenylene vinylene) derivative (formula (40)), a perylene derivative (formula (2)) and a copper phthalocyanine derivative (formulas (20) to (22)), Len derivatives (formula (2)) and phthalocyanine derivatives (formula (19)), perylene derivatives (formula (2)) and amine derivatives (formulas (29) to (35)), perylene derivatives (formula (2)) and poly (Phenylene vinylene) derivative (formula (40)), perylene derivative (formula (2)) and polythiophene derivative (formula (42)), perylene derivative (formula (2)) and polypyrrole derivative (formula (42)), perylene derivative (Formula (2)) and metallocene derivative (Formula (46)), fullerene derivative (Formula (3)) and copper phthalocyanine derivative (Formula (20) to (22)), fullerene derivative (Formula (3)) and amine derivative (Formulas (29) to (35)), fullerene derivatives (Formula (3)) and polythiophene derivatives (Formula (42)), fullerene derivatives (Formula (3)) and polypyrrole derivatives (Formula (42)), Larene derivatives (formula (3)) and metallocene derivatives (formula (46)), cyano group-containing poly (phenylene vinylene) derivatives (formula (4)) and amine derivatives (formulas (29) to (35)), cyano group-containing Poly (phenylene vinylene) derivative (formula (4)) and copper phthalocyanine derivative (formula (20) to (22)), cyano group-containing poly (phenylene vinylene) derivative (formula (4)) and polythiophene derivative (formula (42) ), Cyano group-containing poly (phenylene vinylene) derivative (formula (4)) and polypyrrole derivative (formula (42)), cyano group-containing poly (phenylene vinylene) derivative (formula (4)) and metallocene derivative (formula (46) Etc.) are preferred.
  Examples of such compounds include those represented by the following formulas (62) to (66).

  In the general formulas (62) to (66), R⁶, R⁹, R¹⁰, R¹²~ R¹⁴, R¹⁶And R³⁸May be the same as or different from each other, and are each independently a linear and branched alkyl group having 1 to 10 carbon atoms, alkenyl group, alkoxyl group or aryl group having 6 to 12 carbon atoms, aralkyl group, aryloxy group, An aralkyl group is shown. R^{1 5}Represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. A⁻And B⁻May be the same or different, and each independently represents a halogen anion, ClO.₄ ⁻, BF₄ ⁻, PF₆ ⁻, CH₃COO⁻And CH₃(C₆H₄) SO₃ ⁻The counter anion chosen from is shown. M and n each represent an integer of 1 to 1000, preferably 2 to 500, and k and l represent the number of substitutable substituents of each cyclic hydrocarbon group. It is a range.
  R in the general formulas (62) to (66)¹⁵Specific examples of preferred hydrocarbon groups include hydrocarbon groups such as alkylene, ester group-containing hydrocarbon groups, ether bond-containing hydrocarbon groups, amide bond-containing hydrocarbon groups, thioether bond-containing hydrocarbon groups, and amine bonds. Examples thereof include a hydrocarbon group containing urethane group, a hydrocarbon group containing urethane bond, and a hydrocarbon group containing silyl bond.
  The ester bond-containing hydrocarbon group is represented by the general formula —R—COO—R′— or —R—OCO—R′— (wherein R and R ′ each represent an alkylene having 1 to 8 carbon atoms). And examples of the ether bond-containing hydrocarbon group include those represented by the general formula —R—O—R′— (wherein R and R ′ each represent alkylene having 1 to 10 carbon atoms), The amide bond-containing hydrocarbon group is represented by the general formula -R-CONH-R'- or -R-NHCO-R'- (wherein R and R 'each represent alkylene having 1 to 8 carbon atoms). Examples of the thioether bond-containing hydrocarbon group include those represented by the general formula —R—S—R′— (wherein R and R ′ each represent alkylene having 1 to 10 carbon atoms), and amines As a bond-containing hydrocarbon group A group represented by the general formula —R—NH—R′— (wherein R and R ′ each represent alkylene having 1 to 10 carbon atoms) or a group represented by the general formula —R—NH—Ph— (where R is 1 carbon atom); 10 represents an alkylene having 10 to 10 carbon atoms, and Ph represents an arylene group having 6 to 12 carbon atoms or a substituted arylene group.) The urethane bond-containing hydrocarbon group may be represented by the general formula -R-OCONH-R'- or -R. -NHCOO-R'- (wherein R and R 'each represents an alkylene having 1 to 8 carbon atoms), and the silyl bond-containing hydrocarbon group is represented by the general formula -R-Si (R " )₂-R'- (R and R 'each represent an alkylene having 1 to 8 carbon atoms, and R "represents a methyl group or an ethyl group).
  Among these, specific examples of these compounds include the following compounds.

  Further, examples of the compound having a specific electron-accepting molecular structure include those represented by the following formulas (1 ′) to (18 ′), and examples of the compound having an electron-donating molecular structure include the following formula (19 Examples of ') to (61') can be given.

  In the general formulas (1 ') to (61'), R¹~ R⁹And R¹³~ R⁶⁰Each may be the same or different, and each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxyl group, or an aryl group having 6 to 12 carbon atoms, an aralkyl group, An aryloxy group is shown. R⁴⁴May combine with a cyclopentadienyl ring to form a ring, or may form a group that bridges different cyclopentadienyl rings.
  R¹⁰~ R¹²Each may be the same or different, and each independently represents a hydrogen atom, halogen atom, cyano group, nitro group, hydroxyl group, amino group, carboxyl group, acetyl group, formyl group, linear or branched carbon number 1 to 10 alkyl groups, alkenyl groups, alkoxyl groups, alkylthio groups, alkyloxycarbonyl groups, or aryl groups, aralkyl groups, and aryloxy groups having 6 to 12 carbon atoms.
  In the same structural formula, a plurality of R¹~ R⁶⁰May be the same or different.
  A⁻And B⁻May be the same or different, and each independently represents a halogen anion, ClO.₄ ⁻, BF₄ ⁻, PF₆ ⁻, CH₃COO⁻And CH₃(C₆H₄) SO₃ ⁻The counter anion chosen from is shown.
  M and n each represent an integer of 1 to 1000, preferably 2 to 500, and k and l represent the number of substitutable substituents of each cyclic hydrocarbon group. It is a range.
  M¹Represents a metal atom such as Cu, Zn, Co, Fe, Ti, Mg, Ni, Mo, Os, Ru. M²Represents an alkali metal or alkaline earth metal such as Li, Na, Mg, and Ca. M³Is Cr, Co, Fe, Mg, Ni, Os, Ru, V, X—Hf—Y, X—Mo—Y, X—Nb—Y, X—Ti—Y, X—V—Y or X—Zr. -Y is shown. In addition, X and Y here represent hydrogen, a halogen, or a C1-C12 alkyl group, and may mutually be same or different.
  Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, and hexyl. Group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Examples of the alkenyl group include vinyl group, allyl group, isopropenyl group, butyryl group, pentylenyl group, hexenyl group and the like. As the group, methoxy group, ethoxy group, propoxy group, i-propoxy group, butoxy group, s-butoxy group, t-butoxy group, pentoxy group, isopentoxy group, neopentyloxy group, t-pentyloxy group, hexyloxy Group, isohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group Group, decyloxy group and the like, as aryl group, phenyl group, xylyl group, tolyl group, cumenyl group, naphthyl group and the like, as aralkyl group, benzyl group, trimethyl group and the like as aryloxy group, A phenoxy group, a tolyloxy group, etc. are mentioned.
  Specific examples of the compound having an electron-accepting molecular structure and the compound having an electron-donating molecular structure include polyacetylene, polypyrrole, polypyridine, poly-p-phenylene, poly-p-phenylene sulfide, polyphenylene vinylene, poly (2,5 -Dihexyloxy-1,4-phenylenevinylene), poly (2,5-dioctyloxy-1,4-phenylenevinylene), poly (2-methoxy-5- (2'-ethylhexyloxy) -1,4-phenylenevinylene) ) And the compounds (69) to (131) shown below are preferred.

  Suitable combinations of the electron-accepting molecular structure and the electron-donating molecular structure include fullerene derivatives (the above formula (3 ′)) and poly (phenylene vinylene) derivatives (the above formula (40 ′)), cyano group-containing poly (phenylene Vinylene derivatives (formula (4 ′) above) and poly (phenylene vinylene) derivatives (formula (40 ′) above), viologen derivatives (formula (1 ′) above) and amine derivatives (formulas (29 ′) to (35 above) ')), A viologen derivative (the above formula (1')) and a metallocene derivative (the above formula (46 ')), a viologen derivative (the above formula (1')) and a polythiophene derivative (the above formula (42 ')), a viologen derivative (Formula (1 ′)) and polypyrrole derivative (formula (42 ′)), viologen derivative (formula (1 ′)) and poly (phenylene vinylene) derivative (formula (40 )), Perylene derivatives (the above formula (2 ′)) and copper phthalocyanine derivatives (the above formulas (20 ′) to (22 ′)), perylene derivatives (the above formula (2 ′)) and phthalocyanine derivatives (the above formula (19 ′)) )), Perylene derivatives (the above formula (2 ′)) and amine derivatives (the above formulas (29 ′) to (35 ′)), perylene derivatives (the above formula (2 ′)) and poly (phenylene vinylene) derivatives (the above formula (40 ′)), a perylene derivative (the above formula (2 ′)) and a polythiophene derivative (the above formula (42 ′)), a perylene derivative (the above formula (2 ′)) and a polypyrrole derivative (the above formula (42 ′)), A perylene derivative (the above formula (2 ′)) and a metallocene derivative (the above formula (46 ′)), a fullerene derivative (the above formula (3 ′)) and a copper phthalocyanine derivative (the above formulas (20 ′) to (22 ′)), Fullerene Conductor (formula (3 ′)) and amine derivative (formula (29 ′) to (35 ′)), fullerene derivative (formula (3 ′)) and polythiophene derivative (formula (42 ′)), fullerene derivative (Formula (3 ′)) and polypyrrole derivative (formula (42 ′)), fullerene derivative (formula (3) ′) and metallocene derivative (formula (46 ′)), cyano group-containing poly (phenylene vinylene) Derivatives (above formula (4 ′)) and amine derivatives (above formulas (29 ′) to (35 ′)), cyano group-containing poly (phenylene vinylene) derivatives (above formula (4 ′)) and copper phthalocyanine derivatives (above formulas) (20 ′) to (22 ′)), a cyano group-containing poly (phenylene vinylene) derivative (the above formula (4 ′)) and a polythiophene derivative (the above formula (42 ′)), a cyano group-containing poly (phenylene vinylene) Len) derivatives (formula (4 ′) above) and polypyrrole derivatives (formula (42) ′ above), cyano group-containing poly (phenylene vinylene) derivatives (formula (4 ′) above) and metallocene derivatives (formula (46 ′ above)) Etc.) are preferred.
  Further, the compound (A) having both the electron donating molecular structure and the electron accepting molecular structure dispersed in the polymer constituting the photoelectric conversion layer, or the compound (B) or electron having the electron donating molecular structure. It is desirable that the compound (C) having a receptive molecular structure further has conductivity. Whether or not these compounds have conductivity can be easily determined by a conventional method. For example, these compounds can be discriminated by doping and then measuring the electrical conductivity by a conventional method. Usually, electrical conductivity is 10^-6-10⁶S / m, preferably 10^-4-10⁵A thing of about S / cm is desirable.
  In the present invention, a compound (A) having both an electron-donating molecular structure and an electron-accepting molecular structure in a polymer constituting the photoelectric conversion layer, and / or a compound (B) having an electron-donating molecular structure and electron accepting The compound (C) having an ionic molecular structure is dispersed. The dispersion method is not particularly limited, and examples thereof include a dispersion method using a homogenizer, a ball mill, a bead mill, a sand mill, a two-roll, a three-roll, etc., and an appropriate solvent as long as the present invention is not impaired. And a method of dispersing or dissolving each component in the solvent.
  A polymer precursor, a compound (A) having an electron donating molecular structure and an electron accepting molecular structure, and / or a compound (B) having an electron donating molecular structure and a compound having an electron accepting molecular structure (C ) May be polymerized by polymerizing the polymer precursor by a conventional method.
  The conductive substrate for forming this photoelectric conversion layer is not particularly limited as long as conductivity is obtained by an appropriate method, but it is usually produced by laminating a transparent electrode layer on a transparent substrate. The transparent substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like can be appropriately selected according to the purpose. For example, colorless or colored glass, meshed glass, glass block, etc. are used, and colorless. Alternatively, a colored transparent resin may be used. Specifically, polyesters such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, polymethylpentene and the like can be mentioned. In the present invention, the term “transparent” means to have a transmittance of 10 to 100%, and the term “substrate” in the present invention has a smooth surface at room temperature, and the surface is flat or curved. It may be deformed by stress.
  Further, the transparent conductive film for forming the transparent electrode layer is not particularly limited as long as it achieves the object of the present invention. For example, the transparent conductive layer is made of a metal thin film such as gold, silver, chromium, copper, tungsten, or a metal oxide. Examples thereof include a conductive film. Examples of the metal oxide include tin oxide, zinc oxide, and Indium Tin Oxide (ITO (In₂O₃: Sn)), Fluorine doped Tin Oxide (FTO (SnO₂: F)), Aluminum doped Zinc Oxide (AZO (ZnO: Al)), etc. are preferably used. These film thicknesses are usually 100 to 5000 nm, preferably 500 to 3000 nm. The surface resistance (resistivity) is appropriately selected depending on the use of the substrate of the present invention, but is usually 0.5 to 500 Ω / sq, preferably 2 to 50 Ω / sq.
  A method for forming the transparent electrode film is not particularly limited, and a known method is appropriately selected and used depending on the kind of the metal or metal oxide used as the conductive layer. Usually, a vacuum deposition method, an ion plating method is used. The method, CVD, sputtering method or the like is used. In any case, it is desirable that the substrate is formed within a range of 20 to 700 ° C.
  Moreover, you may provide a semiconductor layer between a conductive substrate and a photoelectric converting layer as needed. Examples of materials used for manufacturing the semiconductor layer include Bi.₂S₃, CdS, CdSe, CdTe, CuInS₂, CuInSe₂, Fe₂O₃, GaP, GaAs, InP, Nb₂O₅, PbS, Si, SnO₂TiO₂, WO₃ZnO, ZnS, etc., preferably CdS, CdSe, CuInS₂, CuInSe₂, Fe₂O₃, GaAs, InP, Nb₂O₅, PbS, SnO₂TiO₂, WO₃ZnO, and a plurality of these may be used in combination. Particularly preferably TiO₂ZnO, SnO₂, Nb₂O₅And most preferably TiO₂ZnO.
  The semiconductor used may be single crystal or polycrystalline. As the crystal system, anatase type, rutile type, brookite type and the like are mainly used, and anatase type is preferable. A known method can be used for forming the semiconductor layer.
  As a method for forming the semiconductor layer, the semiconductor nanoparticle dispersion, the sol solution, or the like can be obtained by coating on a substrate by a known method. The coating method in this case is not particularly limited, and examples include a method of obtaining a thin film by a casting method, a spin coating method, a dip coating method, a bar coating method, and various printing methods including a screen printing method. .
  The thickness of the semiconductor layer is arbitrary, but is 0.5 μm or more and 50 μm or less, preferably 1 μm or more and 20 μm or less.
  Furthermore, in the photoelectric conversion element of this invention, an electron barrier layer and / or a hole transport layer, a hole barrier layer, and / or an electron transport layer, and a protective layer can also be provided as needed. The electron barrier layer and / or hole transport layer is usually provided between the anode and the photoelectric conversion layer, and the hole barrier layer and / or electron transport layer is usually provided between the cathode and the photoelectric conversion layer. An example of these layer structures is shown in FIG.
  The material used for the electron barrier layer and the hole transport layer only needs to have either a function of transporting photogenerated holes or a function of blocking photogenerated electrons. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds Examples thereof include conductive polymers such as copolymers, thiophene oligomers and polythiophenes.
  The electron barrier layer and / or the hole transport layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  The electron barrier layer and / or hole transport layer can be formed by vacuum deposition, LB method, ink jet method, or a method in which the above materials are dissolved or dispersed in a solvent (spin coating method, casting method, dip coating). Law).
  In the case of the coating method, the above material may be dissolved or dispersed together with the resin component to prepare a coating solution. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, Polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, polyvinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy Resin, silicon resin, etc. can be used. The film thicknesses of the electron barrier layer and the hole transport layer are not particularly limited, but are usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.
  The material used for the hole blocking layer and / or the electron transporting layer only needs to have either a function of transporting photogenerated electrons or a function of blocking holes generated by light. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl. Pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, phthalocyanine derivatives, metal complexes (metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as a ligand), etc. It is done.
  The hole blocking layer and / or the electron transporting layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  The hole barrier layer and / or electron transport layer can be formed by vacuum deposition, LB, ink jet, or a method in which the above materials are dissolved or dispersed in a solvent (spin coating, casting, dip coating). Law).
  In the case of a coating method, the above material may be dissolved or dispersed together with the resin component to prepare a coating solution. As this resin component, the same thing as the case of the electron barrier layer and / or hole transport layer mentioned above can be used. The film thickness of the hole barrier layer and / or the electron transport layer is not particularly limited, and is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.
  The protective layer has a function of preventing substances that promote device deterioration such as moisture and oxygen from entering the device. As a material for the protective layer, metal (In, Sn, Pb, Au, Cu, Ag, Al, Ti, Ni, etc.), metal oxide (MgO, SiO, SiO, etc.)₂, Al₂O₃, GeO, NiO, CaO, BaO, Fe₂O₃, Y₂O₃TiO₂Etc.), metal fluoride (MgF)₂, LiF, AlF₃, CaF₂Etc.), polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least A copolymer obtained by copolymerizing a monomer mixture containing one kind of comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0.1 % Moisture-proof material or the like can be used.
  The method for forming the protective layer is not particularly limited, and is a vacuum deposition method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating). Method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, ink jet method and the like can be applied.
  The conductive film formed on the thin film of the photoelectric conversion layer includes metals such as aluminum, magnesium, gold, silver, platinum, indium, copper, and chromium, alloys such as magnesium: silver, conductive carbon and silver. And metal pastes such as gold and copper.
  As a method for forming this conductive film, a known method is appropriately selected and used depending on the above-mentioned materials used for the conductive film. Usually, dry film formation such as vacuum deposition, ion plating, CVD or sputtering is used. In addition to the spin coating method, the dip coating method, the bar coating method, the dispenser method, various printing methods such as a screen printing method can be exemplified.
  The film thickness of the conductive film is usually 100 to 5000 μm, preferably 500 to 3000 μm. The surface resistance (resistivity) is appropriately selected depending on the use of the photoelectric conversion element of the present invention, but is usually 0.5 to 500 Ω / sq, preferably 2 to 50 Ω / sq.
  Further, as another embodiment of the photoelectric conversion device of the present invention, a counter substrate, a counter substrate, a compound (A) having an electron donating molecular structure and an electron accepting molecular structure, and / or an electron donating molecular structure are used. It can also take the form which laminates | stacks the photoelectric converting layer and conductive substrate which consist of the polymer in which the compound (B) which has and the compound (C) which has an electron-accepting molecular structure disperse | distributed.
  Examples of the counter electrode substrate include a support substrate having conductivity by itself, or a substrate in which a conductive film is formed on the support substrate.
  The support substrate is not particularly limited, and materials, thicknesses, dimensions, shapes, and the like can be appropriately selected according to the purpose. The support substrate may or may not be electrically conductive. In addition to metals such as gold and platinum, for example, colorless or colored glass, meshed glass, glass blocks, etc. are used, and the substrate has colorless or colored transparency. Resin may be used. Specifically, polyesters such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, polymethylpentene and the like can be mentioned.
  In addition, the board | substrate in this invention has a smooth surface at normal temperature, The surface may be a plane or a curved surface, and may deform | transform by stress. Also, the surface of the support substrate is made of metal such as gold or platinum,₂O₃: Sn, SnO₂: F, ZnO: Al or the like can be formed into a counter electrode substrate by forming a thin film by a known method such as vacuum deposition, electron beam vacuum deposition, or sputtering.
  When a counter electrode substrate is used, an electrolyte layer may be provided between the photoelectric conversion layer and the counter electrode substrate. The electrolyte layer is an ion conductive material containing at least one substance selected from (a) a polymer matrix, (b) a plasticizer, and (c) a supporting electrolyte. c) or (d) Reversible redox properties are exhibited by a redox agent.
  The material that can be used as the polymer matrix is not particularly limited as long as a solid state or a gel state is formed by the polymer matrix alone, or by the addition of a plasticizer, the addition of a supporting electrolyte, or the addition of a plasticizer and a supporting electrolyte. In general, so-called polymer compounds that are generally used can be used.
  Specific examples of the polymer compound exhibiting characteristics as the polymer matrix include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, acrylic acid, methacrylic acid, methyl acrylate, Examples thereof include polymer compounds obtained by polymerizing or copolymerizing monomers such as ethyl acrylate, methyl methacrylate, and styrene polyvinylidene fluoride. These polymer compounds may be used alone or in combination.
  As the plasticizer, any solvent can be used as long as it is generally used in electrochemical cells and batteries. Specifically, acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, ethylene carbonate, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethoxy Ethane, propiononitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, ethyldimethyl phosphate, tributyl phosphate, phosphorus Tripentyl acid, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, phosphoric acid Tridecyl, tris phosphate (trifluoromethyl), tris phosphate (pentafluoroethyl), triphenyl polyethylene glycol phosphate, polyethylene glycol, and the like can be used. In particular, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulfolane, Trimethyl phosphate and triethyl phosphate are preferred. One plasticizer may be used alone, or two or more plasticizers may be mixed and used.
  As the supporting electrolyte, salts, acids, alkalis and room temperature molten salts that are usually used in the field of electrochemistry or the field of batteries can be used.
  The salt is not particularly limited, and examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts; quaternary ammonium salts; cyclic quaternary ammonium salts; quaternary phosphonium salts. preferable.
  Specific examples of salts include halogen ions and SCN.⁻, ClO₄ ⁻, BF₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, And (C₂F₅SO₂)₃C⁻Li salt, Na salt, or K salt having a counter anion selected from
  Halogen ion, SCN⁻, ClO₄ ⁻, BF₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, And (C₂F₅SO₂)₃C⁻A quaternary ammonium salt having a counter anion selected from: (CH₃)₄NBF₄, (C₂H₅)₄NBF₄, (N-C₄H₉)₄NBF₄, (C₂H₅)₄NBr, (C₂H₅)₄NClO₄, (N-C₄H₉)₄NClO₄, CH₃(C₂H₅)₃NBF₄, (CH₃)₂(C₂H₅)₂NBF₄, (CH₃)₄NSO₃CF₃, (C₂H₅)₄NSO₃CF₃, (N-C₄H₉)₄NSO₃CF₃,Moreover,

Etc. Halogen ion, SCN⁻, ClO₄ ⁻, BF₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, And (C₂F₅SO₂)₃C⁻A phosphonium salt having a counter anion selected from: (CH₃)₄PBF₄, (C₂H₅)₄PBF₄, (C₃H₇)₄PBF₄, (C₄H₉)₄PBF₄Etc.
  Moreover, these mixtures can also be used suitably.
  The acids are not particularly limited, and inorganic acids and organic acids can be used. Specifically, sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like can be used.
  The alkalis are not particularly limited, and any of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used.
  The room temperature molten salt is not particularly limited, but the room temperature molten salt in the present invention is a salt made of an ion pair that is melted at room temperature (that is, a liquid form) consisting of only an ion pair that does not contain a solvent component. In general, it indicates a salt composed of an ion pair having a melting point of 20 ° C. or lower and being liquid at a temperature exceeding 20 ° C.
  The room temperature molten salt can be used alone or in combination of two or more.
  Examples of the room temperature molten salt include the following.

(Here, R represents an alkyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. X⁻Is halogen ion, SCN⁻, ClO₄ ⁻, BF₄ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, And (C₂F₅SO₂)₃C⁻Represents a counter anion selected from )

(Wherein R1 and R2 each represent an alkyl group having 1 to 10 carbon atoms (preferably a methyl group or an ethyl group) or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms (preferably a benzyl group). May be the same or different, and X⁻Represents a counter anion, specifically, a halogen ion or SCN.⁻, ClO₄ ⁻, BF₄ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, (C₂F₅SO₂)₃C⁻Etc. )

(Where R³, R⁴, R⁵, R⁶Each represents an alkyl group having 1 or more carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms (such as a phenyl group), or a methoxymethyl group, and may be the same or different. X⁻Represents a counter anion, specifically, a halogen ion or SCN.⁻, ClO₄ ⁻, BF₄ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, (C₂F₅SO₂)₃C⁻Etc. )
  The amount of the supporting electrolyte used is not particularly limited and is arbitrary, but is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more in the electrolyte layer, and It can be contained in an amount of 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less.
  Next, the redox material will be described.
  The redox material can perform a reversible electrochemical oxidation-reduction reaction and does not particularly limit the type thereof. As the redox material, only one of an oxidant and a reductant may be used, or the oxidant and the reductant may be mixed and added at an appropriate molar ratio.
  Further, an oxidation-reduction pair of these polymer matrix, plasticizer, and supporting electrolyte may be added so that the polymer matrix, plasticizer, and supporting electrolyte exhibit electrochemical responsiveness. Examples of materials that exhibit such properties include halogen ions and SCN.⁻, ClO₄ ⁻, BF₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, PF₆ ⁻, AsF₆ ⁻, CH₃COO⁻, CH₃(C₆H₄) SO₃ ⁻, And (C₂F₅SO₂)₃C⁻In addition to metallocenium salts such as ferrocenium having a counter anion selected from halogen, halogens such as iodine, bromine and chlorine can also be used.
  The electrolyte can further contain other components. Examples of other components that can be contained include ultraviolet absorbers. Although it does not specifically limit as an ultraviolet absorber which can be used, Organic UV absorbers, such as a compound which has a benzotriazole skeleton and a compound which has a benzophenone skeleton, are mentioned as a typical thing.
  As the compound having a benzotriazole skeleton, for example, a compound represented by the following general formula (132) is preferably exemplified.

  In the general formula (132), R⁸¹Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. R⁸¹The substitution position of is the 4-position or 5-position of the benzotriazole skeleton, but the halogen atom and the alkyl group are usually located at the 4-position. R⁸²Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. R⁸³Represents an alkylene group or alkylidene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group.
  Specific examples of the compound represented by the general formula (132) include 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid. 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzeneethanoic acid, 3- (2H-benzotriazol-2-yl) -4-hydroxybenzene Ethanoic acid, 3- (5-methyl-2H-benzotriazol-2-yl) -5- (1-methylethyl) -4-hydroxybenzenepropanoic acid, 2- (2′-hydroxy-5′-methylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl) benzotriazole, 2- (2′-hydroxy-3 ′ , 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 3- (5-chloro-2H) -Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester and the like.
  Preferred examples of the compound having a benzophenone skeleton include compounds represented by the following general formulas (133) to (135).

  In the general formulas (133) to (135), R⁹², R⁹³, R⁹⁵, R⁹⁶, R⁹⁸And R⁹⁹Are the same or different from each other and represent a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or an alkoxy group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, and a butoxy group.
  R⁹¹, R⁹⁴And R⁹⁷Represents an alkylene group or alkylidene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group.
  p1, p2, p3, q1, q2, and q3 each independently represent an integer of 0 to 3.
  Preferred examples of the compound having a benzophenone skeleton represented by the general formulas (133) to (135) include 2-hydroxy-4-methoxybenzophenone-5-carboxylic acid and 2,2′-dihydroxy-4-methoxybenzophenone. -5-carboxylic acid, 4- (2-hydroxybenzoyl) -3-hydroxybenzenepropanoic acid, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy -2'-carboxybenzophenone, etc. .
  Of course, two or more of these can be used in combination.
  The use of the ultraviolet absorber is optional, and the amount used is not particularly limited, but when used, it is 0.1% by mass or more, preferably 1% by mass or more in the electrolyte. It is desirable to make it contain in the quantity of the range of 20 mass% or less, Preferably it is 10 mass% or less.
  The electrolyte layer may be manufactured as an electrolyte film. The manufacturing method of an electrolyte film is demonstrated below.
  The electrolyte film is obtained by molding a mixture obtained by blending optional components such as a plasticizer, a supporting electrolyte, a redox material, and an ultraviolet absorber into a polymer matrix component, if desired, by a known method. I can do it. The molding method in this case is not particularly limited, and examples thereof include extrusion molding, a method obtained in a film state by a casting method, a spin coating method, and a dip coating method.
  Extrusion molding can be performed by a conventional method, and a polymer matrix and an optional component such as a plasticizer, a supporting electrolyte, a redox material, and an ultraviolet absorber are mixed, heated and melted, and then formed into a film.
  For the casting method, polymer matrix and plasticizer, supporting electrolyte, redox material, UV absorber and other optional components are mixed, and the viscosity is adjusted with an appropriate diluent. The film can be formed by applying and drying. As the coater, a doctor coater, a blade coater, a rod coater, a knife coater, a reverse roll coater, a gravure coater, a spray coater, and a curtain coater can be used, and they can be selectively used depending on the viscosity and the film thickness.
  For the spin coating method, a polymer matrix and optional components such as plasticizer, supporting electrolyte, redox material, and UV absorber are mixed, and the viscosity is adjusted with an appropriate diluent and applied with a commercially available spin coater. The film can be formed by drying.
  For the dip coating method, a polymer matrix and an optional component such as a plasticizer, a supporting electrolyte, a redox material, and an ultraviolet absorber are mixed, and the viscosity is adjusted with an appropriate diluent to prepare a mixture solution. A film can be formed by lifting the substrate from the mixture solution and then drying.
  The electrolyte film obtained by the above method has an ionic conductivity of usually 1 × 10 at room temperature.^-7S / cm or more, preferably 1 × 10^-6S / cm or more, more preferably 1 × 10^-5S / cm or more is shown. The ionic conductivity can be obtained by a general method such as a complex impedance method.
  The thickness of the electrolyte film is not particularly limited, but the lower limit is usually 1 μm or more, preferably 10 μm or more, and the upper limit is usually 3 mm or less, preferably 1 mm or less.

In the photoelectric conversion element of the present invention, the occurrence of phase separation in the photoelectric conversion layer is suppressed, and the efficiency of light separation in the photoelectric conversion layer is improved because the efficiency of charge separation is improved. Is possible.
In addition, the photoelectric conversion element of the present invention can be manufactured relatively easily, and has features such as a low environmental load during manufacture and disposal.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

On a 5 cm square ITO glass (transparent conductive glass in which a Sn-doped In ₂ O ₃ film is formed on a glass substrate) having a surface resistance of 10 Ω / sq and cleaned by alkali cleaning and plasma-ozone cleaning, polymethyl methacrylate ( A coating solution in which 200 mg of a compound represented by the following formula having both an electron-accepting molecular structure and an electron-donating molecular structure is dispersed in a solution obtained by dissolving 500 mg of FLUKA, Mw = about 200,000) in 10 g of chloroform is spin-coated. did. The photoelectric conversion layer was produced by fully drying. The layer thickness was about 4.5 μm. When the surface state of the photoelectric conversion layer was observed, a uniform and non-cloudy film was formed. Moreover, although the obtained photoelectric converting layer was left at 80 degreeC for 20 hours, the change was not recognized especially.
Next, about 100 nm of aluminum was laminated on this photoelectric conversion layer at 1.33 × 10 ⁻³ Pa (1 × 10 ⁻⁵ Torr) at (30 （/ s) to produce a photoelectric conversion element.
When this element was irradiated with light from a 100 W tungsten lamp made uniform through a diffusion plate from the glass substrate side and the current value at the time of short circuit was measured, a current value of 4 μA was obtained, and the characteristics of a good photoelectric conversion element were obtained. It was confirmed that

On a 5 cm square ITO glass (transparent conductive glass in which a Sn-doped In ₂ O ₃ film is formed on a glass substrate) having a surface resistance of 10 Ω / sq and cleaned by alkali cleaning and plasma-ozone cleaning, polymethyl methacrylate ( Fullerene (C ₆₀ ) 200 mg as a compound having an electron-accepting molecular structure and a compound having an electron-donating molecular structure in a solution prepared by dissolving 500 mg of FLUKA Co., Mw = about 200,000) in 10 g of chloroform A coating solution in which 100 mg (poly (2,5-dihexyloxy-1,4-phenylene vinylene), manufactured by ALDRICH) was dispersed was spin-coated. The photoelectric conversion layer was produced by fully drying. The layer thickness was about 5 μm. When the surface state of the photoelectric conversion layer was observed, a uniform and non-cloudy film was formed. Moreover, although the obtained photoelectric converting layer was left to stand at 80 degreeC for 20 hours, the change was not recognized especially.
Next, about 100 nm of aluminum was laminated on this photoelectric conversion layer at 1.33 × 10 ⁻³ Pa (1 × 10 ⁻⁵ Torr) at (30 （/ s) to produce a photoelectric conversion element.
When this element was irradiated with light from a 100 W tungsten lamp made uniform through a diffusion plate from the glass substrate side and the current value at the time of short circuit was measured, a current value of 2.1 μA was obtained, and a good photoelectric conversion element was obtained. It was confirmed that the characteristics were exhibited.

On a 5 cm square ITO glass (transparent conductive glass having a Sn-doped In ₂ O ₃ film formed on a glass substrate) having a surface resistance of 10 Ω / sq and cleaned by alkali cleaning and plasma-ozone cleaning, poly [(3 , 4-ethylenedioxy) -2,5-thiophene] .polystyrenesulfonic acid dispersion (“BaytronP” manufactured by Bayer, solid content: 1.3%), spin-coated and vacuum dried at 150 ° C. for 2 hours. A coating layer having a thickness of 100 nm was formed. Further thereon, polymethyl methacrylate (FLUKA Co., Mw = about 200,000) a _{C 60} to 500mg of the compound having an electron-accepting molecular structure in a solution prepared by dissolving in chloroform 10 g 200 mg, and an electron-donating molecular structure A coating solution in which 100 mg of the compound (a) used in Example 2 was dispersed as a compound having spin coating was spin-coated. The photoelectric conversion layer was produced by fully drying. The layer thickness was about 5 μm. When the surface state of the photoelectric conversion layer was observed, a uniform and non-cloudy film was formed. Moreover, although the obtained photoelectric converting layer was left to stand at 80 degreeC for 20 hours, the change was not recognized especially.
Next, about 100 nm of Al was laminated | stacked on this photoelectric converting layer by 1.33 * 10 < ^-3 > Pa (1 * 10 < ^-5 > Torr) at (30 [deg.] / S), and the photoelectric conversion element was produced.
This element was irradiated with light from a 100 W tungsten lamp made uniform through a diffusion plate from the glass substrate side, and the current value at the time of short circuit was measured. As a result, a current value of 3.5 μA was obtained, and a good photoelectric conversion element was obtained. It was confirmed that the characteristics were exhibited.

On a 5 cm square ITO glass (transparent conductive glass having a Sn-doped In ₂ O ₃ film formed on a glass substrate) having a surface resistance of 10 Ω / sq and cleaned by alkali cleaning and plasma-ozone cleaning, poly [(3 , 4-ethylenedioxy) -2,5-thiophene] .polystyrenesulfonic acid dispersion (“BaytronP” manufactured by Bayer, solid content: 1.3%), spin-coated and vacuum dried at 150 ° C. for 2 hours. A coating layer having a thickness of 100 nm was formed. Furthermore, an electron-accepting molecular structure and an electron-donating molecular structure are combined in a solution in which 500 mg (poly (2,5-dihexyloxy-1,4-phenylenevinylene), ALDRICH) is dissolved in 10 g of chloroform. A coating solution in which 200 mg of the compound (b) represented by the following formula was dispersed was spin-coated. The photoelectric conversion layer was produced by fully drying. The layer thickness was about 5 μm. When the surface state of the photoelectric conversion layer was observed, a uniform and non-cloudy film was formed. Moreover, although the obtained photoelectric converting layer was left to stand at 80 degreeC for 20 hours, the change was not recognized especially.
Next, about 100 nm of Al was laminated | stacked on this photoelectric converting layer by 1.33 * 10 < ^-3 > Pa (1 * 10 < ^-5 > Torr) at (30 [deg.] / S), and the photoelectric conversion element was produced.
When this element was irradiated with light from a 100 W tungsten lamp made uniform through a diffusion plate from the glass substrate side and the current value at the time of short circuit was measured, a current value of 4.2 μA was obtained, and a good photoelectric conversion element was obtained. It was confirmed that the characteristics were exhibited.

On a 5 cm square ITO glass (transparent conductive glass having a Sn-doped In ₂ O ₃ film formed on a glass substrate) having a surface resistance of 10 Ω / sq and cleaned by alkali cleaning and plasma-ozone cleaning, poly [(3 , 4-ethylenedioxy) -2,5-thiophene] .polystyrenesulfonic acid dispersion (“BaytronP” manufactured by Bayer, solid content: 1.3%), spin-coated and vacuum dried at 150 ° C. for 2 hours. A coating layer having a thickness of 100 nm was formed. Furthermore, a compound having an electron-accepting molecular structure in a solution prepared by dissolving 500 mg of (poly (2,5-dihexyloxy-1,4-phenylenevinylene), ALDRICH) in 10 g of chloroform has the following formula: A coating liquid in which 200 mg of the compound (c) represented by the formula (1) and 100 mg of the compound (d) represented by the following formula were dispersed as a compound having an electron donating molecular structure was spin coated. The photoelectric conversion layer was produced by fully drying. The layer thickness was about 5 μm. When the surface state of the photoelectric conversion layer was observed, a uniform and non-cloudy film was formed. Moreover, although the obtained photoelectric converting layer was left to stand at 80 degreeC for 20 hours, the change was not recognized especially.
Next, about 100 nm of Al was laminated | stacked by 1.33 * 10 < ^-3 > Pa (1 * 10 < ^-5 > Torr) and (30 * / s) on this photoelectric converting layer, and the photoelectric conversion element was produced.
When this element was irradiated with light from a 100 W tungsten lamp made uniform through a diffusion plate from the glass substrate side and the current value at the time of short circuit was measured, a current value of 4.5 μA was obtained, and a good photoelectric conversion element was obtained. It was confirmed that the characteristics were exhibited.

FIG. 1 is an example of a layer structure as a photoelectric conversion element in the present invention.
FIG. 2 is another example of a layer structure as a photoelectric conversion element in the present invention.

Claims (4)

A photoelectric conversion element comprising a photoelectric conversion layer in which an organic compound (A) having both an electron-donating molecular structure and an electron-accepting molecular structure is dispersed in a polymer. The present invention relates to a photoelectric conversion element comprising a photoelectric conversion layer in which an organic compound (B) having an electron-donating molecular structure and an organic compound (C) having an electron-accepting molecular structure are dispersed in a polymer. The photoelectric conversion element according to claim 1, wherein the polymer is a conductive polymer compound. The photoelectric conversion element according to claim 2, wherein the polymer is a conductive polymer compound.

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